US20090114539A1 - Mixture potential sensor for measuring a gas concentration and a method for the production thereof - Google Patents

Mixture potential sensor for measuring a gas concentration and a method for the production thereof Download PDF

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Publication number
US20090114539A1
US20090114539A1 US12/090,803 US9080306A US2009114539A1 US 20090114539 A1 US20090114539 A1 US 20090114539A1 US 9080306 A US9080306 A US 9080306A US 2009114539 A1 US2009114539 A1 US 2009114539A1
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electrode
solid
state
platinum
mixture
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Abandoned
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US12/090,803
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English (en)
Inventor
Joerg Ziegler
Mario Roessler
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Robert Bosch GmbH
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Robert Bosch GmbH
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Assigned to ROBERT BOSCH GMBH reassignment ROBERT BOSCH GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ROESSLER, MARIO, ZIEGLER, JOERG
Publication of US20090114539A1 publication Critical patent/US20090114539A1/en
Abandoned legal-status Critical Current

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4075—Composition or fabrication of the electrodes and coatings thereon, e.g. catalysts

Definitions

  • the invention concerns a sensor for measuring the concentration of a gas component in a gas mixture according to the generic term of claim 1 .
  • the invention further concerns a method for the production of an electrode of such a sensor according to the generic term of claim 6 .
  • a familiar sensor that is used for the regulation of the air-fuel ratio of combustion mixtures for combustion engines originates for example from DE 101 56 248 C1.
  • Such a sensor presents a heated zirconium oxide element with a cavity, which is connected with the exhaust gas of the combustion engine by a diffusion barrier as well as a reference electrode, an inner pump electrode and an outer pump electrode. All electrodes consist of platinum (cermet).
  • the reference electrode is arranged in an air reference channel or is created by a so-called pumped reference.
  • the pump current between the inner and the outer pump electrode is so adjusted by a control loop that a constant preset Nernst voltage between the reference electrode and the inner pump electrode is measured throughout.
  • the quantity of the required pump current depends on the oxygen content that is in the exhaust gas and therefore on the lambda-value.
  • the signal of such a sensor also called wide band lambda probe (LSU) is basically stable.
  • FIG. 1 schematically shows the signal course during the occurrence of such a ⁇ 1-waviness, which is labeled with the reference sign 10 in FIG. 1 .
  • the invention is therefore based on the task to improve such a sensor, as described above, and to provide a method for its production, so that the interfering ⁇ 1-waviness is reduced.
  • This task is solved by a sensor with the characteristics of the independent claim 1 as well as by a method with the characteristics of claim 6 .
  • the solid-state is created by a platinum-gold-alloying.
  • the solid-state creates a ceramic electrode.
  • the solid-state is created by an oxidic electrode.
  • the solid-state consists of a platinum electrode, on which a deposition of gold takes place.
  • the deposition of gold can either occur by a galvanic displacement of gold on the platinum electrode or by a decomposition of a gold salt, for example HAuCL 4 , in a post-firing-process on the platinum electrode.
  • the solid-state can also be produced by a platinum-gold paste that is treated by a cofiring.
  • the platinum-gold paste is spread on the outside of the zirconium-oxide and is transformed into a solid-state by the cofiring.
  • FIG. 1 schematically a ⁇ 1-waviness of the pump current over the time, as it is already known from the state of the art;
  • FIG. 2 schematically cut a sensor making use of this invention
  • FIG. 3 schematically the pump current over the time at a sensor element with a platinum outer electrode
  • FIG. 4 the pump current over the time at a sensor element with a platinum outer electrode, which was galvanically gold-plated by a deposition of gold.
  • the sensor that is shown in FIG. 2 embraces a zirconium oxide element 120 , which is heated by a heater that has been established by heating elements 190 .
  • This zirconium oxide element presents a cavity 130 , which is connected with the exhaust gas of e.g. a (not shown) combustion engine by a diffusion barrier 150 , as well as a reference electrode 140 , an inner pump electrode 170 and an outer pump electrode 160 .
  • the reference electrode 140 and the inner pump electrode 170 consist of platinum (cermet).
  • the reference electrode 140 is located in an air reference channel 180 and can be also built as a so-called pumped reference.
  • oxygen can be pumped out of the cavity 130 or pumped into the cavity 130 .
  • the outer pump electrode 160 is electrically positive towards the inner pump electrode, oxygen is for example pumped out of the cavity 130 .
  • With a growing voltage the current now rises until it is limited by the post flow through the diffusion barrier 150 (limiting current area).
  • a (not shown) control loop regulates the pump current I p between the inner pump electrode 170 and the outer pump electrode 160 , so that a constant, preset Nernst voltage UN is always measured between the reference electrode 140 and the inner pump electrode 170 .
  • the quantity of the required pump current I p depends on the oxygen content that is present in the exhaust gas and therefore on the ⁇ -value.
  • the signal of this sensor which is also known as a wide band lambda probe, is basically constant.
  • the invention provides that the outer pump electrode 160 is built by a solid-state, which leads to the creation of mixture potentials.
  • the invention is based on the knowledge that the observed ⁇ 1-waviness is built by the interaction of probe and control unit, whereby it is considered that also the outer pump electrode 160 is capacitive coupled onto the reference electrode 140 .
  • the size of the jump is influenced by the jump of the Nernst voltage, which depends only on the oxygen partial pressure when using a pure platinum electrode.
  • the potential of mixture potential electrodes depends on the other side on the concentration of several exhaust gas components. For this reason the jumps in the signal of the pump current or the pump voltage, which are called as ⁇ 1-waviness, do not occur when using a mixture potential electrode as an outer pump electrode 160 .
  • Mixture potential electrodes are principally not balance electrodes.
  • the thermo dynamic balance at the inner pump electrode 170 has to be adjusted for determining the ⁇ -value. This does not have to be the case at the outer pump electrode 160 , where a gas exchange takes place.
  • the outer pump electrode 160 can be build by a solid-state, which consists of a platinum-gold alloying. It is also possible to build the outer pump electrode 160 as a ceramic or oxidic electrode.
  • the outer pump electrode is thereby implemented, in that a galvanic deposition of gold takes place at a familiar platinum solid-state. It is also possible to modify the platinum electrode by an impregnating process, meaning to impregnate the platinum electrode with an appropriate Au-salt, for example HAuCl 4 and to decompose the Au-salt in a post-firing-process. It is further possible to spread a platinum-gold paste that is transformed by a cofiring in a solid-state, which builds the outer pump electrode 160 , on the zirconium-oxide ceramic. Au-contents of 0.1-10 wt %, especially 1-5 wt % in the platinum-gold-paste proved themselves as advantageous.
  • FIG. 3 shows the signal course of the pump current I p over the time of a sensor, which has a platinum outer electrode as known from the state of the art.
  • the pump current clearly shows here the previously described ⁇ 1-waviness, which is labeled with the reference sign 310 in FIG. 3 .
  • FIG. 4 shows the pump current over the time of the sensor shown in FIG. 3 , whereby the outer electrode was gold-plated by a deposition of gold. After the galvanic gilding of the outer pump electrode 160 a ⁇ 1-waviness does not occur anymore.
  • LSU wide band lambda probe
  • an outer electrode that is build as a mixture potential electrode was previously described. It shall be understood that the invention is not limited to such a wide band lambda probe. It is principally also possible to provide the pump probe (LSP) with a mixture potential pump electrode, especially with a platinum-gold electrode, in order to minimize signal discontinuities.
  • LSP pump probe

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Measuring Oxygen Concentration In Cells (AREA)
US12/090,803 2005-10-18 2006-09-22 Mixture potential sensor for measuring a gas concentration and a method for the production thereof Abandoned US20090114539A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005049775A DE102005049775A1 (de) 2005-10-18 2005-10-18 Sensor zur Messung der Konzentration einer Gaskomponente in einem Gasgemisch und Verfahren zur Herstellung einer Elektrode eines solchen Sensors
DE102005049775.6 2005-10-18
PCT/EP2006/066650 WO2007045541A1 (de) 2005-10-18 2006-09-22 Mischpotenzialsensor zur messung einer gaskonzentration und verfahren zu dessen herstellung

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US20090114539A1 true US20090114539A1 (en) 2009-05-07

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US12/090,803 Abandoned US20090114539A1 (en) 2005-10-18 2006-09-22 Mixture potential sensor for measuring a gas concentration and a method for the production thereof

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US (1) US20090114539A1 (ja)
EP (1) EP1941268B1 (ja)
JP (1) JP4827924B2 (ja)
CN (1) CN101292155B (ja)
DE (2) DE102005049775A1 (ja)
WO (1) WO2007045541A1 (ja)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100243447A1 (en) * 2009-03-30 2010-09-30 Ngk Insulators, Ltd. Pumping electrode of gas sensor, method of manufacturing conductive paste, and gas sensor
US20110314898A1 (en) * 2008-07-10 2011-12-29 Dirk Liemersdorf Sensor element and method for determining gas components in gas mixtures, and use thereof
US20130081448A1 (en) * 2010-06-15 2013-04-04 Robert Bosch Gmbh Circuit assembly for operating a gas probe
US20130305812A1 (en) * 2011-01-28 2013-11-21 Torsten Reitmeier Sensor Element And A Method For Detecting A Parameter Of A Gas Mixture In A Gas Chamber
US9011659B2 (en) 2011-04-08 2015-04-21 Continental Automotive Gmbh Sensor apparatus for detecting a gas concentration and a particle concentration of an exhaust gas
EP2980574A1 (en) * 2014-07-29 2016-02-03 NGK Insulators, Ltd. Gas sensor, method of producing conductive paste, and method of manufacturing gas sensor
US9891139B2 (en) 2014-12-03 2018-02-13 Ngk Insulators, Ltd. Catalyst deterioration diagnosis system and catalyst deterioration diagnosis method
US9939348B2 (en) 2014-12-03 2018-04-10 Ngk Insulators, Ltd. Catalyst deterioration diagnosis method
US10196958B2 (en) 2014-12-03 2019-02-05 Ngk Insulators, Ltd. Catalyst deterioration diagnosis method
US10876993B2 (en) 2015-12-24 2020-12-29 Ngk Insulators, Ltd. Ammonia gas sensor and method for measuring concentration of ammonia gas

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009046317A1 (de) * 2009-11-03 2011-05-05 Robert Bosch Gmbh Sensor zum Detektieren wenigstens eines ersten Mediums in einem Mediengemisch aus wenigstens dem ersten und einem zweiten Medium, Verfahren zum Herstellen des Sensors sowie Chip mit dem Sensor
DE102013208939A1 (de) * 2013-05-15 2014-11-20 Robert Bosch Gmbh Mikromechanische Sensorvorrichtung
CN110672703A (zh) * 2019-11-19 2020-01-10 成都凯圣捷科技有限公司 用于焦炉煤气的氧气检测系统

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US6193053B1 (en) * 2000-03-31 2001-02-27 Mark K. Gaalswyk Concentric auger feeder
US6334946B1 (en) * 1998-05-28 2002-01-01 Ngk Spark Plug Co., Ltd. Method of stabilizing pump current in gas sensor
US20020011410A1 (en) * 1997-09-22 2002-01-31 Ngk Spark Plug Co., Ltd. Gas sensor, gas sensor system using the same, and method of manufacturing a gas sensor
US20020023838A1 (en) * 1998-07-23 2002-02-28 Schneider Jens Stefan Gas sensor and corresponding production method

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DE19932048A1 (de) * 1999-07-09 2001-01-11 Bosch Gmbh Robert Meßfühler zur Bestimmung einer Konzentration von Gaskomponenten in Gasgemischen
DE10030939A1 (de) * 2000-06-24 2002-01-17 Bosch Gmbh Robert Pt/Au-Elektroden zum Abpumpen von O¶2¶ und Verfahren zu ihrer Herstellung
CN2468048Y (zh) * 2001-02-27 2001-12-26 中国科学院海洋研究所 氧化还原电位的复合电极
DE10163942A1 (de) * 2001-12-22 2003-07-10 Bosch Gmbh Robert Abgassonde
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US5720864A (en) * 1995-09-28 1998-02-24 Matsushita Electric Industrial Co., Ltd. Electrochemical device
US20020011410A1 (en) * 1997-09-22 2002-01-31 Ngk Spark Plug Co., Ltd. Gas sensor, gas sensor system using the same, and method of manufacturing a gas sensor
US6334946B1 (en) * 1998-05-28 2002-01-01 Ngk Spark Plug Co., Ltd. Method of stabilizing pump current in gas sensor
US20020023838A1 (en) * 1998-07-23 2002-02-28 Schneider Jens Stefan Gas sensor and corresponding production method
US6193053B1 (en) * 2000-03-31 2001-02-27 Mark K. Gaalswyk Concentric auger feeder

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110314898A1 (en) * 2008-07-10 2011-12-29 Dirk Liemersdorf Sensor element and method for determining gas components in gas mixtures, and use thereof
US8940144B2 (en) * 2008-07-10 2015-01-27 Robert Bosch Gmbh Sensor element and method for determining gas components in gas mixtures, and use thereof
US8366893B2 (en) 2009-03-30 2013-02-05 Ngk Insulators, Ltd. Pumping electrode of gas sensor, method of manufacturing conductive paste, and gas sensor
US20100243447A1 (en) * 2009-03-30 2010-09-30 Ngk Insulators, Ltd. Pumping electrode of gas sensor, method of manufacturing conductive paste, and gas sensor
US20130081448A1 (en) * 2010-06-15 2013-04-04 Robert Bosch Gmbh Circuit assembly for operating a gas probe
US9983157B2 (en) * 2010-06-15 2018-05-29 Robert Bosch Gmbh Circuit assembly for operating a gas probe
US9829457B2 (en) * 2011-01-28 2017-11-28 Continental Automotive Gmbh Sensor element and a method for detecting a parameter of a gas mixture in a gas chamber
US20130305812A1 (en) * 2011-01-28 2013-11-21 Torsten Reitmeier Sensor Element And A Method For Detecting A Parameter Of A Gas Mixture In A Gas Chamber
US9011659B2 (en) 2011-04-08 2015-04-21 Continental Automotive Gmbh Sensor apparatus for detecting a gas concentration and a particle concentration of an exhaust gas
EP2980574A1 (en) * 2014-07-29 2016-02-03 NGK Insulators, Ltd. Gas sensor, method of producing conductive paste, and method of manufacturing gas sensor
US10168295B2 (en) 2014-07-29 2019-01-01 Ngk Insulators, Ltd. Gas sensor, method of producing conductive paste, and method of manufacturing gas sensor
US9891139B2 (en) 2014-12-03 2018-02-13 Ngk Insulators, Ltd. Catalyst deterioration diagnosis system and catalyst deterioration diagnosis method
US9939348B2 (en) 2014-12-03 2018-04-10 Ngk Insulators, Ltd. Catalyst deterioration diagnosis method
US10196958B2 (en) 2014-12-03 2019-02-05 Ngk Insulators, Ltd. Catalyst deterioration diagnosis method
US10876993B2 (en) 2015-12-24 2020-12-29 Ngk Insulators, Ltd. Ammonia gas sensor and method for measuring concentration of ammonia gas

Also Published As

Publication number Publication date
EP1941268B1 (de) 2011-01-26
JP2009511928A (ja) 2009-03-19
DE502006008826D1 (de) 2011-03-10
JP4827924B2 (ja) 2011-11-30
DE102005049775A1 (de) 2007-04-19
CN101292155B (zh) 2013-02-06
WO2007045541A1 (de) 2007-04-26
CN101292155A (zh) 2008-10-22
EP1941268A1 (de) 2008-07-09

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Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:ZIEGLER, JOERG;ROESSLER, MARIO;REEL/FRAME:021652/0753;SIGNING DATES FROM 20080825 TO 20080902

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